JPS593999B2 - N-(O-alkyl-S-shibouzoku-(thiono)-thiolphosphoryl)-iminogysan alkyl ester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a particularly novel N
- [0-alkyl-5-aliphatic (thiono)-thiolphosphoryl]iminoformic acid alkyl esters, active compositions in the form of mixtures of said compounds with solid and liquid dispersible carrier vehicles, and their compounds and their use in novel methods for combating pests, in particular insects and mites,
These are the objectives to be provided; other objectives will become apparent from the specification and examples.

35 From German Publication Specification No. 2116690, N-[
It is known that 0-5-dimethyl-thionothiolphosphoryl]-iminoformic acid ethyl ester (compound A) has insecticidal and acaricidal properties.

The present invention is based on the formula [wherein R is alkyl having 1 to 6 carbon atoms, k is alkenyl or alkynyl having up to 6 carbon atoms, lower alkylmercapto-lower alkyl or N-alkyl-carbamoylmethyl, X is oxygen or sulfur, and Alk is an alkyl group having 1 to 6 carbon atoms]
-[0-Alkyl-S-aliphatic mono(thiono)-thiolphosphoryl]-iminoformic acid alkyl ester.

Preferably, R is straight-chain or branched lower alkyl having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary mono-butyl or tertiary-butyl. , Alk is lower alkyl having 1 to 3 carbon atoms, and k is lower alkenyl or alkynyl having 2 to 4 carbon atoms, N-
Mono-methylcarbamoyl-methyl, N-mono-ethyl or ethylmercaptoethyl.

Surprisingly, the compounds according to the invention are better insecticidal agents than known N-[0.S-dialkyl(thiono)-thio-phosphoryl]-iminoformic acid alkyl esters having a similar structure and the same type of activity. (particularly systemic) and has acaricidal activity.

They therefore represent a real benefit to the industry.
The present invention also relates to the formula [wherein X. R and R/ have the above meanings]
An alkyl-(thiono)-thiol phosphoric acid ester amide is reacted with an orthomonoformic acid alkyl ester of the formula:
) is also provided.

When using 0-methyl-S-ethylmercaptoethylthiol phosphoric acid diesteramide and orthoformic acid ethyl ester as starting materials, the reaction process is represented by the following reaction formula: Examples of compounds of formulas () and () includes: O-methyl-S-allyl-, 0
Ethyl-S-allyl-, 0-n-propyl-S-allyl-
, O-isopropyl-S-allyl-, On-butyl-S
-allyl-, O-sec-butyl-S-allyl-,
0-isobutyl-S-allyl-, 0-tert-butyl-S-allyl-, O-methyl-S-propargyl-,
O-ethyl-S-propargyl, O-n-propyl S
-propargyl-1, 0-isopropyl-S-propargyl-1, 0-n-butyl-S-propargyl-1, 0-sec-butyl-1-S-propargyl-1, O-isobutyl-S-propargyl-0-tert-butyl-S-propargyl 0-Methyl-S-(N-monomethylcarbamoylmethyl)-thiol phosphoric acid diesteramide and the corresponding thiono homologues, as well as the methyl, ethyl or propyl esters of orthoformic acid.

Compounds of formula () are known from the literature and can be prepared by known methods, for example DE 1216835 and DE 6911925.

Compounds of formula () and methods for their preparation are also known. The process according to the invention can also be carried out using solvents, the term also including simple diluents. However, preferably no solvent is used for the reaction. If desired, an acid catalyst, e.g. p
-Toluene-sulfonic acid can be used.

The reaction temperature can vary within a wide range.

Generally, the reaction is carried out at about 100-200°C, preferably at about 140°C.
Performed at ~160°C. Generally, the reaction is carried out under normal pressure.

In practicing the process, the reactants are combined in the absence of a solvent, where the orthoformate is typically 10-20%
used in excess.

The mixture is boiled under reflux for 5-6 hours, during which time the alcohol formed is distilled off. Distill the residue. The compounds of the invention are most often obtained as colorless or slightly yellow oils which cannot be distilled without significant decomposition. If they cannot be distilled, they are "distilled and separated"
That is, volatile impurities can be separated by heating at a moderately elevated temperature for a long period of time under reduced pressure. Refractive index is particularly suitable for their identification. As mentioned above, the compounds of the invention are characterized by a pronounced insecticidal and acaricidal effect against crop pests, sanitary pests and stored crop pests.

They are suckers and pests of insects and mites (Acari).
It has good activity against na).

They have at the same time a slight phytotoxicity and a toxicity to warm-blooded animals that is 5-10 times lower than the compounds from which they are derived. The compounds of the invention can therefore be successfully used as insecticides in the crop protection and stored product protection and hygiene fields. Sap-sucking insects include insects of the aphid family (Aphidae), such as the green peach aphid (My.
zuspersicae), Bean aphid (Bean
aphid) (Dnralis fabae), wheat aphid (RhOpalOsiphumpadi)
, MacrOsiphu
mpisi), potato aphid (POtatOaphi)
d) (MacrOsiphumsOlanifOlii
), Currentgall
aphid) (CryptOmyzu8kOrsche
lti), ROsyappl
eaphid (Sappaphismali), Hyalopterusarund
inis) and Cherry black fly (Cherry
black-Fly) (Myzuscerasi);
In addition, insects of the family Mealyptidae and the family Mealyptidae (COccina), such as the white scale insect (A
spidiOtushederae), Softscale (Lecaniumhespe)
ridum) and Grape Mealybug (Grape
mealybug) (PseudOcOccusmar
itimus); Thripsipidae insects (ThysanO
ptera), e.g. Herci
nOthripsfemOralis); Hemiptera insects such as Beetbug (Piesma
quadrata), Red
eOttOnbug) (Dysdercusinter
medius), bed bugs (Cimexlectu)
larius), Assassinb
ug) (RhOdniusprOlixus) and Chagas'Bug (TriatO
mainfestans); and cicada insects (Ci
cadas), such as Eusthelis bilobataus (Eu
scelisbilObatus) and NephOtettix bipunctatus (NephOtettixbip)
unctatus).

Insects that feed on insects include, in particular, insects of the order Lepidoptera, such as the diamondback moth (P.
lutellamaculipennis), gypsy moth (Lymantriadispar), BrOwn-TailmOth (EuprO
ctischrysOrrhOea) and Prunus ctischrys (
MalacOsOmaneustria); and Mamestrabrassicae, Katsutowa. -CutwOrm (AgrOtisseget
um), Large White Butterfly (Largewhi)
tebutterfly) (Pierisbrassi)
cae), Small winter moss (Smallwin)
termOth) (Cheimat Obiabruma
ta), Green Oak Tortorixmoss (Gre
enOaktOrtrixmOth), (Tortri
xviridana), Foal Army Worm (Fa
llarn] YwOrm) (LaphygTnafru
giperda), Spodoptera trifoliata (PrOdenia)
litura), ErminemOth
) (HypOnOmeutapadella), Mediterranean
flOurmOth) (Niel from Ephestiak)
la), and honey hemlock (Galleriamello
nella).

Also, those classified as insects include Coleoptera (CO).
leOptera), e.g. Granary Weevil (G
ranaryweevil) (SitOphilusg)
ranarius-Calandragranaria
), Colorado Beetle
)(LeptinOtarsadecemllneat
a), DOOkbeetle (Ga
s'TrOphysaviridula), Mustardbeetle (Phaed
OncOchleariae), Brasssum beetle (
BlOssOmbeetle) (Meligethes
aeneus), raspberry beetle (Raspbe
rrybeetle) (ByturstOmentO
sus), bean weevil (Bruchidiu
s-AcanthOscelidesObjects
), Dermestesfri
schi), Khaprabeet
le) (TrOgOdermagranarium),
TribOllumcastane
um), Kokuzo (Ca] Andra or SitOph
illuszeamais), St.
egObiumpaniceum), the Japanese white beetle (TenebriOmOlitOr), and the saw-whet beetle (Oryzaephi1ussu).
rinamensis); as well as species of insects that live in the soil, such as Wire-WOrm.
(family AgriOtes), and Kotsukukafueru (CO
ckchafer) (MelOlOnthamelOl
Ontha); insects of the Order Cockroaches, such as Blatella germanica
), American cockroach (Periplaneta amer)
icana), Madeira Kotsukurochi (Madeir)
acOckrOach) (LeucOphea or Rh
yparObiamadeirae), Oriental Cotscroach (0rienta1c0ckr0ach) (
Blatta Orientals), GiantcOckrOack (Bla
bcrus giganteus) and BlackgiantcOckrO
ach) (Blaberus fuscus); and HenschOu
tedeniaflezvitta): also Orthoptera (0rth0ptera), such as HOusecricket (AchetadO
mesticus); insects of the order Termite, such as Eastern subterranean termite (Eastern subterranean termite);
bterrameantermite) (Retieu
and Hymenoptera, such as the Garden Ant (Lasius niger). Insects of the order Diptera are mainly flies, such as Drosophila melanogaster (
DrOsOphilamelanOgaster), Mediterranean Fruit Fry (Mediterranean Fruit Fry)
eanfruitfly) (Ceratitiscape
itata), house fly (MuscadOmestic)
a), Eanniacanicular
is), PhOrmiaregina
, Bluebottlefly
)(CallphOraer37thrOcepha
la) and stable fly (StOmOxyscalcitr
ans): as well as Gnat species, such as Aedesaegypti, Northern House Mosquito
itO) (Culexpipiens) and Malaria Mosquito (AnO
phelessstephcnsi).

Those classified in the order Acari include, in particular, members of the family Tetranychidae, such as the two-spotted spider mite (Tetranychustelarius-Tetr).
anychusalthaeae=Tetranych
usurticae) and apple spider mites (Parate
trannychuspiilOsusOPanOnych
usulmi), Gallmite,
For example, blackcurrant galmite (Blackcurrant galmite)
rantgallmite) (EriOphyesri
bis) and dust mites, such as dust mites (
HemitarsOnemuslatus) and cyclamen dust mite (TarsOnemuspallidu)
s); Finally, take (Tick), such as Relapsing fever take (Relapsing fever take);
tick) (0rnith0d0rusm0ubata
) is included.

When the compounds are used against health-damaging pests, especially flies, power and stored crop pests, they have a significant residual activity on wood and soil, and against alkalis in lime-treated materials. It is characterized by good stability. The active compounds according to the invention may optionally be used as common inert (i.e. phytocompatible or herbicidally inert) pesticide diluents or fillers, i.e. in common pesticide formulations or compositions. Types of diluent that can be used,
carriers or fillers, such as dispersible carrier vehicles for common pesticides, such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, dusting powders, liniments, wettable powders, powders,
It can be used in the form of granules, etc. These are known methods,
For example, the active compound may be transferred to a dispersible liquid diluent carrier for common pesticides, optionally using carrier vehicle auxiliaries such as surfactants (including emulsifiers and dispersants) for pesticides, and Organic solvents can be used as auxiliary solvents, for example when water is used as diluent. Common carrier vehicles for this purpose include primarily: aerosol propellants that are gaseous at ambient temperature and pressure, such as Freon; inert dispersible liquid diluent carriers, such as inert organic solvents. ,
For example, aromatic hydrocarbons (e.g. benzene, toluene,
xylenes, alkylnaphthalenes, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzene, etc.), cycloalkanes (e.g. cyclohexane, etc.), paraffins (e.g. petroleum or mineral oil fractions)
, chlorinated aliphatic hydrocarbons (e.g. methylene chloride, chloroethylene, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, glycol, etc.), and their ethers and esters (
(e.g., glycol monomethyl ether), amines (e.g., ethanolamine, etc.), amides (e.g., dimethylformamide, etc.), sulfoxides (e.g., dimethyl sulfoxide, etc.), acetonitrile, ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) ) and/or water; and an inert, dispersible, finely divided solid carrier;
For example, crushed natural minerals (e.g. kaolin, clay, alumina, silica, chiyok, i.e. calcium carbonate,
talc, attapulgite, montmorillonite, diatomaceous earth, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.). On the other hand, common carrier substances which can be used as surfactants, for example, are mainly emulsifiers, such as nonionic and/or anionic emulsifiers (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, etc., and especially alkylaryl polyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersants, such as lignin, sulfite waste liquor, methyl cellulose, etc. The active compounds may be present alone or in combination with each other and/or optionally in solid and/or liquid dispersible carrier vehicles and/or other known compatible active agents, in particular plant protection agents, as well as other fungicides. Insecticides and acaricides, or mixtures of rodenticides, fungicides, bactericides, nematicides, herbicides, disinfectants, growth retardants, etc., or solutions, emulsions, etc. prepared therefrom, e.g. They can be used in the form of dosage specific formulations for individual applications such as suspensions, powders, liniments and granules.

For commercial market formulations, they contain substantially from about 0.1 to 95% by weight of active compound, and preferably 0.1% to 95% by weight of active compound.
Carrier composition mixtures suitable for direct or field application are contemplated in which the active compound is present in an amount between 5 and 90% by weight, generally about 0.0001% of the mixture by weight. It is intended to be present in an amount of ~10, preferably 0.01-1% by weight. Therefore, the present invention
For example, (1) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid, such as an inert organic solvent and/or water (preferably a surface-actively effective amount of carrier). It includes any composition consisting of a mixture of common dispersible carrier vehicles, such as vehicle auxiliaries, e.g. surfactants, e.g. and which generally ranges from about 0.0001 to 95% of the mixture.
, and preferably 0.01 to 95% by weight. The active compound can be applied according to the known ultra-concentrated low volume application methods, i.e. usually by applying the compound in liquid form, or by applying the compound in finely divided form (e.g. below 50 to 100 microns). It can also be used by applying techniques such as spraying onto crops by means of an airplane, eg by airplane, through highly effective spraying equipment, i.e. in atomized form.

About 2-31 at most? ．． Small amounts up to 15-10007/ha are required, but often about 15-10007/ha,
Preferably, 40-6007/ha is sufficient. This method comprises about 20 to about 95% by weight of active compound or 10% by weight of active compound.
Highly concentrated liquid compositions containing 0% active substance, for example about 20-100% by weight of active compound together with a liquid carrier vehicle, can be used. Furthermore, the present invention provides for the application of insecticidal or acaricidal amounts to at least one of (a) insects, (b) mites, and (c) their habitat, i.e. the area to be protected. It also encompasses a method of selectively killing, controlling or controlling pests, such as insects and mites, which comprises applying an effective amount of a particular active compound of the invention, alone or together with a carrier vehicle as described above, to .

The formulations or compositions of the present invention can be prepared in a conventional manner, for example by spraying, spraying, evaporative application, granulation, dusting, liquid application, jet application, watering, injection, dou fumigation, etc.
Applicable. The concentration of the particular active compound employed in admixture with the carrier vehicle will, of course, depend on the intended application.

Therefore, in special cases it is also possible to use concentrations higher or lower than those mentioned above. synthesis of specific novel compounds of the invention;
The unexpected superiority and remarkable activity are illustrated by the following test examples.

Test Example 1 Green peach aphid (Myzus) test (contact action) Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To prepare a suitable formulation of the active compound, 1.
Parts by weight of active compound are mixed with the above amount of solvent containing the above amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage plants (Brassica) heavily infested with green peach aphid (Myzuspersicae)
Oleracea) were sprayed with the active compound formulation until drippings.

After a certain period of time, the degree of mortality (%) was measured: 100%
means that all aphids are killed, and 0% means that no aphids are killed.

The active compound, the concentration of the active compound, the evaluation time and the results are shown in Table 1 below.

Test Example 2 Bean Aphid (DOralis) test (systemic activity)
Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylaryl polyglycol ether To prepare a suitable formulation of the active compound, 1 part by weight of the active compound is combined with the above amount containing the above amount of emulsifier. and the concentrate was diluted with water to the desired concentration.

Bean plants (Iciafaba) heavily infested with bean aphid (DOralis fabae) were sprayed with a preparation of the active compound in such a way that it penetrated into the soil without wetting the beanstalk leaves.

The active compound was absorbed from the soil by the beanstalk and reached the infected leaves. After a certain time, the degree of mortality (%) was determined.

100% means all the aphids are killed, and 0% means none are killed.

The active compound, the concentration of the active compound, the evaluation time and the results are shown in Table 2 below.

Experimental Example 3 Tetranychus Test/Resistance Solvent: 3 parts by weight of acetone emulsifier: 1 part by weight of alkylaryl polyglycol ether In order to prepare a suitable formulation of the active compound, 1 part by weight of the active compound was added. The above amount of emulsifier was mixed with the above amount of solvent and the resulting concentrate was diluted with water to the desired concentration.

A beanstalk (PhaseOlusv) that is about 10 to 30 degrees tall.
ulgaris) with a drop of the active compound preparation! - The liquid was sprayed until

Two-spotted spider mites (Tetra) in all stages of growth are present on these beanstalks.
nychusurticae).
After a certain period of time, the effectiveness of the active compound formulation was determined by counting the number of dead mites.

The degree of effect obtained was expressed as a percentage: 100% means the death of all two-spotted spider mites, O% means no death.
The active compound, the concentration of the active compound, the evaluation time and the results are shown in Table 3 below.

Test Example 4 Granary Weevil (SitOphilusgran)
arius) test/LDlOO solvent: 2 parts by weight of acetone of active compound were dissolved in 1000 parts by volume of solvent and the resulting solution was diluted with solvent to the desired concentration.

2.5 ml of the active compound solution was added to a 9.5 crfL diameter (
:f) Samples were collected with a pipette into a Petri dish with loose paper spread on the bottom.

Do not cover the Petri dish until the solvent has completely evaporated. ▲
The amount of active compound per square meter of paper depends on the concentration of the active compound solution. Approximately 25 test pests were placed in a Petri dish and covered with a glass lid. One and three days after the start of the test, the condition of the test pests was observed, and the degree of death was expressed as a percentage.

The active compounds, their concentrations and results are shown in Table 4 below.

Test Example 5 Housefly (Muscad Omestica)
Test/LTlOO Solvent: 2 parts by weight of acetone of active compound were dissolved in 1000 parts by volume of solvent and the resulting solution was diluted with solvent to the desired low concentration.

2.5 ml of the active compound solution was added to a tube with a diameter of 9.5 mm (FLf
) The sample was collected with a pipette into a Petri dish lined with P paper at the bottom.

Do not cover the Petri dish until the solvent has completely evaporated. The amount of active compound per square meter of paper varies depending on the concentration of the active compound solution. Approximately 25 test pests were placed in a Petri dish and covered with a glass lid. The condition of the test pests was continuously observed, and the time required to achieve 100% killing effect was measured.

The active compounds, their concentrations and results are shown in Table 5 below. The following Preparation Examples illustrate the method for preparing the active compounds according to the invention. Preparation Example 1 The starting materials used could be prepared, for example, in the following way:
637 2-chloroethylthioether, 250ml
of the sodium salt of O-ethylthiol phosphate esteramide in methanol.

The mixture was stirred at 70°C for 1 hour. After cooling the reaction mixture, it was diluted with 200 ml (:f),' of water, extracted three times with 200 ml each of chloroform, and the organic layer was dried. After drying, the solvent was distilled off and the residue was heated under reduced pressure. 106V (93% of theoretical value) O
-Ethyl-S-ethylmercaptoethylthiol phosphoric acid diesteramide (refractive index n-1, 5334) was obtained.

The resulting oil solidifies when recrystallized from a mixture of ethyl acetate and ligroin, and its melting point is 50-53°C.
It was hot. The following compounds could be produced in a similar manner.

Production Example 367 (0.2 mol) of O-ethyl-S-allylthiol-phosphoric acid diesteramide, 30f of O〉1rin formic acid ethyl ester, and 17 of p-toluenesulfonic acid were refluxed at 100°C. (10? Bigley column) for 30 minutes.

The mixture was then distilled to yield 35y (74% of theory) of N-(0-ethyl-S-aryruthiolphosphoryl).
-Iminoformic acid ethyl ester (boiling point 96°C/0.017
F! 1Hg1 refractive index NY=1.4962) was obtained.
The following compounds could be produced in a similar manner.

Embodiments of the present invention and related matters are described below.

1. Formula [wherein R is alkyl having 1 to 6 carbon atoms, k is alkenyl or alkynyl having up to 6 carbon atoms, lower alkylmercapto-lower alkyl or N-alkyl-carbamoylmethyl, and X is the number of oxygen atoms or sulfur;
and Alk is an alkyl group having 1 to 6 carbon atoms].

2. R is lower alkyl, k is lower alkenyl, lower alkynyl, N-monomethylcabamoylmethyl, N-
A compound according to 1 above, which is monoethylcarbamoylmethyl, methylmercaptoethyl or ethylmercaptoethyl, and Alk is lower alkyl.

3. The compound has the formula N(0-ethyl-S-arylthiolphosphoryl)
- A compound according to 1 above, which is iminoformic acid ethyl ester.

4. The compound has the formula N(0-methyl-S-arylthiolphosphoryl)
- A compound according to 1 above, which is iminoformic acid ethyl ester.

5. A compound according to 1 above, wherein the compound is N(0-ethyl-S-propargylthiolphosphoryl)-iminoformic acid ethyl ester of the formula.

6. A compound according to 1 above, wherein the compound is N(0-methyl-S-propargylthiolphosphoryl)-iminoformic acid ethyl ester.

7. A compound according to 1 above, wherein the compound is N[0-ethyl-S-(N-monomethylcarbamoylmethyl)-thiolphosphoryl]-iminoformic acid ethyl ester.

8. Formula [wherein R is alkyl having 1 to 6 carbon atoms, k is alkenyl or alkynyl having up to 6 carbon atoms, lower alkylmercapto-lower alkyl or N-alkyl-carbamoylmethyl, and X is oxygen or sulfur and Alk is an alkyl group having 1 to 6 carbon atoms. The ester has the formula [wherein R. R' and X have the above meanings]
A method characterized by reacting with an alkyl-(thiono)thiol monophosphate ester amide.

9. An insecticidal, acaricidal or nematicidal composition comprising an insecticidal, acaricidal or nematicidal effective amount of the compound according to 1 above, mixed with a diluent.

0. A method for controlling insect, mite or nematode pests, which comprises applying an insecticidal, acaricidal or nematocidal effective amount of a compound according to 1 above to the insect, mite or nematode pest or their habitat.

1. The compound is N(0-ethyl-S-allyruthiolphosphoryl)-
Iminoformic acid ethyl ester, N(0-methyl-S-aryruthiolphosphoryl)-iminoformic acid ethyl ester, N(0-ethyl-S-propargylthiolphosphoryl)-iminoformic acid ethyl ester, N(0-methyl-
S-propargyl-thiolphosphoryl)-iminoformic acid ethyl ester, or N[0-ethyl-S-(N-monomethylcarbamoylmethyl)-thiolphosphoryl]-
The method according to 10 above, which is iminoformic acid ethyl ester.

Claims (1)

[Claims] 1 Formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R is alkyl having 1 to 6 carbon atoms, and R' is alkenyl, alkynyl, or lower alkyl having up to 6 carbon atoms. Mercapto-lower alkyl or N-alkyl-
carbamoylmethyl, X is oxygen or sulfur,
In producing the phosphorylated iminoformic acid alkyl ester, Alk is an alkyl group having 1 to 6 carbon atoms, there are formulas, mathematical formulas, chemical formulas, tables, etc. [In the formula, Alk has the above meaning. The orthoformic acid alkyl ester with the formula ▲ has a numerical formula, chemical formula, table, etc. ▼ [wherein R, R' and X have the above meanings]
A method characterized by reacting with an alkyl-(thiono)thiol-phosphate ester amide.